JP5986291B2 - Poly (phenylene ether) compositions, articles and methods - Google Patents

Description

  Poly (phenylene ether) is a type of plastic known for superior water resistance, dimensional stability, inherent flame retardancy, high oxygen permeability and oxygen / nitrogen selectivity. Properties such as strength, stiffness, chemical resistance and heat resistance can be adjusted by mixing poly (phenylene ether) with various other plastics, for example sanitary equipment, switchboards, automotive parts and insulation for wires and cables Can meet the requirements of a wide range of consumer goods such as the body.

  Blends of poly (phenylene ether) and polystyrene are commercially available and are used in injection molded articles such as appliances and housings for household electronic devices. It would be desirable to prepare a blend of poly (phenylene ether) and polystyrene using recycled polystyrene material to reduce waste and save energy. US Pat. No. 5,264,487 to Scobbo et al. Includes poly (phenylene ether) and polystyrene, and further includes an acrylonitrile-butadiene-styrene copolymer and a copolymer of an olefin such as ethylene and an epoxy compound such as glycidyl methacrylate. , A plastic composition is described. The poly (phenylene ether), polystyrene and acrylonitrile-butadiene-styrene copolymer can be supplied in the form of a mixed recycle stream. However, due to the low compatibility of acrylonitrile-butadiene-styrene copolymers with poly (phenylene ether) and polystyrene, olefin-epoxy copolymers must be used as compatibilizers. It would be desirable if the complexity and cost associated with the use of such compatibilizers could be avoided.

  US Pat. No. 7,964,675 to Ko et al. Describes a plastic composition comprising recycled poly (phenylene ether) and another recycled plastic, which may in particular be an acrylonitrile-butadiene-styrene copolymer. Has been. In the composition, any recycled plastic that can decompose and form volatile components during plastic composition formation is minimized or eliminated. The Ko et al composition makes maximum use of recycled materials, however, its impact strength is not sufficient for some injection molding applications.

  Accordingly, there is a need for blends of poly (phenylene ether) and polystyrene that retain most of the impact strength of blends prepared with virgin resin while utilizing recycled plastic raw materials.

  In one embodiment, poly (phenylene ether) is greater than 40 to 94.8% by weight, polymerized styrene residue is 5 to 59.8% by weight, and polymerized acrylonitrile, unless otherwise specified. It is a composition containing 0.2 to less than 1.5% by mass of a residue, and the concentration of the secondary aliphatic hydroxyl group is 120 ppm by mass or less.

  Another embodiment is a poly (2,6-dimethyl-1, which has an intrinsic viscosity of 0.35-0.6 dL / g measured in chloroform at 25 ° C., relative to the total weight of the composition, unless otherwise specified. A flame retardant containing 60-80% by mass of 4-phenylene ether), 5-15% by mass of polymerized styrene residue, 0.4-2% by mass of polymerized 1-butene residue, and an organic phosphate. A composition containing 10 to 20% by mass and a polymerized acrylonitrile residue of 0.2 to 1.2% by mass, wherein the concentration of secondary aliphatic hydroxyl groups is 120 ppm by mass or less. .

  Another embodiment is an article comprising the above composition.

  Another embodiment provides poly (phenylene ether) greater than 40 to 94.8% by weight, homopolystyrene 5 to 59.8% by weight, and polymerized acrylonitrile residue, unless otherwise specified, relative to the total weight of the composition. Acrylonitrile homopolymer and / or copolymer in an amount sufficient to supply 0.2 to less than 1.5% by weight of the group, and the concentration of secondary aliphatic hydroxyl groups is 120 ppm by weight. It is a formation method of the composition provided with the step of forming the following compositions.

  These and other embodiments are described in detail below.

  All ranges disclosed herein are inclusive of endpoints, which endpoints can be combined independently of each other. Each of the ranges disclosed herein constitutes a disclosure of any point or sub-range within this disclosure range.

  In the context of describing the present invention (especially in the context of the following claims), the singular forms are intended to include the singular and plural forms unless the context clearly dictates otherwise. Is done. Further, as used herein, terms such as “first” and “second” do not represent any order, amount or importance, but are used to distinguish one component from another. It is what “About” as used in connection with a quantity is intended to include the stated numerical value and has a context-determined meaning (eg, including the degree of error associated with the measurement of a particular quantity). .

  In our investigation of blends of poly (phenylene ether) with homopolystyrene utilizing recycled homopolystyrene, the recycled homopolystyrene contains significant amounts of acrylonitrile copolymer impurities. I found that there are many. High concentrations of these impurities can significantly reduce the impact strength of the polymer blend. We have blended poly (phenylene ether) with homopolystyrene utilizing recycled homopolystyrene by providing specific limits on the amount of polymerized acrylonitrile residues associated with acrylonitrile copolymer impurities, It has been found that blends can be provided that retain most of the desired properties of the corresponding blends prepared from these resins. The composition does not require a compatibilizing agent such as the compatibilized olefin-epoxy copolymer of Scobbo et al. US Pat. No. 5,264,487.

  Accordingly, one embodiment provides poly (phenylene ether) in excess of 40 to 94.8% by weight and polymerized styrene residue in the range of 5 to 59.8% by weight, based on the total weight of the composition, unless otherwise specified. A composition containing 0.2 to less than 1.5% by mass of a polymerized acrylonitrile residue, wherein the concentration of secondary aliphatic hydroxyl groups is 120 ppm by mass or less.

式中、Ｚ^１はそれぞれ独立に、ハロゲン、ヒドロカルビル基が第三級ヒドロカルビルではない未置換または置換Ｃ_１−Ｃ_１２ヒドロカルビル、Ｃ_１−Ｃ_１２ヒドロカルビルチオ、Ｃ_１−Ｃ_１２ヒドロカルビルオキシ、あるいは少なくとも２つの炭素原子がハロゲン原子と酸素原子とを分離しているＣ_２−Ｃ_１２ハロヒドロカルビルオキシであり；Ｚ^２はそれぞれ独立に、水素、ハロゲン、ヒドロカルビル基が第三級ヒドロカルビルではない未置換または置換Ｃ_１−Ｃ_１２ヒドロカルビル、Ｃ_１−Ｃ_１２ヒドロカルビルチオ、Ｃ_１−Ｃ_１２ヒドロカルビルオキシ、あるいは少なくとも２つの炭素原子がハロゲン原子と酸素原子とを分離しているＣ_２−Ｃ_１２ハロヒドロカルビルオキシである。本明細書において、「ヒドロカルビル」は、単独であるいは別の用語の接頭辞、接尾辞またはフラグメントとして使用されたとしても、炭素と水素だけを含む残基を指す。該残基は、脂肪族または芳香族、直鎖、環式、二環式、分枝鎖、飽和または不飽和であってもよい。それはまた、脂肪族、芳香族、直鎖、環式、二環式、分枝鎖、飽和および不飽和炭化水素部分の組み合わせを含んでいてもよい。しかしながら、該ヒドロカルビル残基が置換であると記載された場合、それは任意に、該置換残基の炭素と水素員上にヘテロ原子を含んでいてもよい。従って、置換であると特定的に記載された場合、該ヒドロカルビル残基は、１個または複数個のカルボニル基、アミノ基、水酸基なども含み得、あるいは、ヒドロカルビル残基の骨格内にヘテロ原子を含み得る。一例として、Ｚ^１は、３，５−ジメチル−１，４−フェニル基と酸化重合触媒のジ−ｎ−ブチルアミン成分との反応で形成されたジ−ｎ−ブチルアミノメチル基であってもよい。 The composition includes poly (phenylene ether). Suitable poly (phenylene ethers) include those containing repeating structural units of the following formula:

In which each Z ¹ is independently halogen, unsubstituted or substituted C ₁ -C ₁₂ hydrocarbyl, C ₁ -C ₁₂ hydrocarbylthio, C ₁ -C ₁₂ hydrocarbyloxy, wherein the hydrocarbyl group is not a tertiary hydrocarbyl, or at least C ₂ -C ₁₂ halohydrocarbyloxy in which two carbon atoms separate a halogen atom and an oxygen atom; each Z ² is independently an unsubstituted or hydrogen, halogen, hydrocarbyl group that is not a tertiary hydrocarbyl or substituted _C 1 _{-C 12 hydrocarbyl,} C 1 _{-C 12 hydrocarbylthio,} C 1 _{-C 12} hydrocarbyloxy, or at least two _C 2 _{-C 12} halohydrocarbyloxy carbon atoms separate the halogen and oxygen atoms It is. As used herein, “hydrocarbyl” refers to a residue comprising only carbon and hydrogen, whether used alone or as a prefix, suffix or fragment of another term. The residue may be aliphatic or aromatic, linear, cyclic, bicyclic, branched, saturated or unsaturated. It may also include a combination of aliphatic, aromatic, straight chain, cyclic, bicyclic, branched, saturated and unsaturated hydrocarbon moieties. However, when the hydrocarbyl residue is described as being substituted, it may optionally contain heteroatoms on the carbon and hydrogen members of the substituted residue. Thus, when specifically described as being substituted, the hydrocarbyl residue may also contain one or more carbonyl groups, amino groups, hydroxyl groups, etc., or contain heteroatoms in the skeleton of the hydrocarbyl residue. May be included. As an example, Z ¹ may be a di-n-butylaminomethyl group formed by a reaction between a 3,5-dimethyl-1,4-phenyl group and a di-n-butylamine component of an oxidative polymerization catalyst. .

  In some embodiments, the intrinsic viscosity of the poly (phenylene ether) is 0.2-1 dL / g measured in chloroform at 25 ° C. Within this range, the intrinsic viscosity of the poly (phenylene ether) can be 0.25 to 0.8 dL / g, more specifically 0.25 to 0.7 dL / g, and even more specifically Can be 0.3 to 0.65 dL / g, and even more specifically 0.35 to 0.6 dL / g.

別の例として、未使用ポリ（２，６−ジメチル−１，４−フェニレンエーテル）における下記の構造の分岐フラグメント量は一般に、１００質量ｐｐｍ未満であろう：

これらのフラグメントは、炭素核磁気共鳴分光法で同定および定量できる。 In some embodiments, the poly (phenylene ether) used to prepare the composition is manufactured as opposed to recycled poly (phenylene ether), ie, poly (phenylene ether) that has undergone significant heat treatment. Composed of “unused” poly (phenylene ether), which means The concentration of poly (phenylene ether) rearrangement products such as cross-linked products and branched products in the unused poly (phenylene ether) will generally be lower compared to recycled poly (phenylene ether). For example, the amount of cross-linked fragments of the following structure in virgin poly (2,6-dimethyl-1,4-phenylene ether) will generally be less than 100 ppm by weight:

As another example, the amount of branched fragments of the following structure in virgin poly (2,6-dimethyl-1,4-phenylene ether) will generally be less than 100 ppm by weight:

These fragments can be identified and quantified by carbon nuclear magnetic resonance spectroscopy.

  In some embodiments, the poly (phenylene ether) is essentially free of incorporated diphenoquinone residues. In this context, “essentially free” means that the poly (phenylene ether) molecule comprising residues of diphenoquinone is less than 1% by weight. As described in Hay US Pat. No. 3,306,874, the synthesis of poly (phenylene ether) by oxidative polymerization of monohydric phenol produces not only the desired poly (phenylene ether) but also diphenoquinone as a by-product. Produced as a product. For example, when the monohydric phenol is 2,6-dimethylphenol, 3,3 ', 5,5'-tetramethyldiphenoquinone is produced. The diphenoquinone is typically “re-equilibrated” within the poly (phenylene ether) by heating the polymerization reaction mixture to produce a poly (phenylene ether) containing terminal or internal diphenoquinone residues (ie, , Diphenoquinone is incorporated into the poly (phenylene ether) structure). For example, poly (phenylene ether) is prepared by oxidative polymerization of 2,6-dimethylphenol and poly (2,6-dimethyl-1,4-phenylene ether) and 3,3 ′, 5,5′-tetramethyldi When producing phenoquinone, re-equilibration of the reaction mixture can produce poly (phenylene ether) with incorporated diphenoquinone terminals and internal residues. However, such re-equilibration reduces the molecular weight of poly (phenylene ether). Thus, if a higher molecular weight poly (phenylene ether) is desired, it may be desirable to separate the diphenoquinone from the poly (phenylene ether) without re-equilibrating the poly (phenylene ether) chain. Such separation can be achieved, for example, by precipitating poly (phenylene ether) in a solvent or solvent mixture in which poly (phenylene ether) is insoluble but diphenoquinone is soluble. For example, poly (phenylene ether) is prepared by oxidative polymerization of 2,6-dimethylphenol in toluene to produce poly (2,6-dimethyl-1,4-phenylene ether) and 3,3 ′, 5,5 ′. When producing a toluene solution containing tetramethyldiphenoquinone, poly (2,6-dimethyl-1,4-phenylene ether) essentially free of diphenoquinone is one volume of the toluene solution and methanol or methanol / methanol / Obtained by mixing about 1 to about 4 volumes of water mixture. Alternatively, the amount of diphenoquinone by-product produced during oxidative polymerization is (eg, initiated oxidative polymerization in the presence of less than 10% by weight monohydric phenol and at least 95% by weight for at least 50 minutes). Can be minimized (by adding dihydric phenol) and / or re-equilibration of diphenoquinone into the poly (phenylene ether) chain (eg, isolating the poly (phenylene ether) within 200 minutes after oxidative polymerization is complete) Can be minimized). These methods are described in US Pat. No. 8,025,158B2 to Delsman et al. An alternative method that utilizes the temperature-dependent solubility of diphenoquinone in toluene is that the temperature of the toluene solution containing diphenoquinone and poly (phenylene ether) is about 25, where diphenoquinone is almost insoluble but poly (phenylene ether) is soluble. By adjusting to ° C., insoluble diphenoquinone can be removed by solid-liquid separation (for example, filtration).

  In some embodiments, the poly (phenylene ether) comprises 2,6-dimethyl-1,4-phenylene ether units, 2,3,6-trimethyl-1,4-phenylene ether units, or combinations thereof. . In some embodiments, the poly (phenylene ether) is poly (2,6-dimethyl-1,4-phenylene ether). In some embodiments, the poly (phenylene ether) has an intrinsic viscosity measured in chloroform at 25 ° C. of 0.25 to 0.8 dL / g, specifically 0.25 to 0.7 dL / g. More specifically from about 0.3 to about 0.65 dL / g, even more specifically from 0.35 to 0.6 dL / g poly (2,6-dimethyl-1,4-phenylene ether). )including.

  The poly (phenylene ether) may comprise a molecule having aminoalkyl-containing end group (s) that are typically located in the ortho position relative to the hydroxyl group. The poly (phenylene ether) may be in the form of a homopolymer, copolymer, graft copolymer, ionomer, block copolymer, or a combination comprising at least one of these.

  The composition comprises greater than 40 to 94.8% by weight of poly (phenylene ether), based on its total weight. Within this range, the amount of poly (phenylene ether) can be at least 41 wt%, can be at least 43 wt%, can be at least 45 wt%, or can be at least 50 wt%. Also within this range, the amount of poly (phenylene ether) can be up to 90% by weight, can be up to 85% by weight, can be up to 80% by weight, or can be up to 75% by weight.

The composition includes polymerized styrene residues in addition to poly (phenylene ether). At the time of preparing the composition, the polymerized styrene residue can be supplied in the form of homopolystyrene. Homopolystyrene herein refers to a homopolymer of styrene. Therefore, the residue of any monomer other than styrene is not included in the homopolystyrene. The homopolystyrene may be atactic, syndiotactic or isotactic. In some embodiments, the homopolystyrene is composed of atactic homopolystyrene. In some embodiments, the melt volume flow rate of the homo-polystyrene, compliant with ISO1133, temperature 200 ° C., as measured by a load 5 kg, is 1.5~5cm ^3/10 min.

  The composition contains 5 to 59.8% by mass of polymerized styrene residues based on the total mass. Within this range, the amount of polymerized styrene residue may be 7-50% by weight, specifically 9-40% by weight, more specifically 11-30% by weight, More specifically, it may be 11 to 20% by mass. The amount of polymerized styrene residue is calculated relative to the components used to form the composition. Alternatively, the amount of polymerized styrene residue can be determined by carbon nuclear magnetic resonance spectroscopy.

  The composition comprises polymerized acrylonitrile residues in addition to poly (phenylene ether) and polymerized styrene residues. The amount of polymerized acrylonitrile residues can be less than 0.2-1.5% by weight relative to the total weight of the composition. Within this range, the amount of polymerized acrylonitrile residue may be 0.4-1.4% by weight, specifically 0.6-1.3% by weight, more specifically 0.00. It may be 6-1.2% by weight, and even more specifically 0.6-1% by weight. The amount of polymerized acrylonitrile residues can be determined by carbon nuclear magnetic resonance spectroscopy, gradient polymer elution chromatography, or transmission Fourier transform infrared spectroscopy (transmission FTIR) spectroscopy.

A specific procedure for determining polymerized acrylonitrile residues in a composition by transmission FTIR spectroscopy is as follows. A Perkin Elmer SPECTRUM® 100 spectrometer is used for FTIR measurements. Four calibration standards are prepared containing 0-2.8 wt% polymerized acrylonitrile in a blend of poly (2,6-dimethyl-1,4-phenylene ether) and rubber-modified polystyrene. The polymerized acrylonitrile in the composition is obtained from the incorporation of a styrene-acrylonitrile copolymer containing 31.6% by weight polymerized acrylonitrile and 68.4% by weight polymerized styrene. The calibration composition is injection molded into plaques, and from this plaques a Specac constant thickness film making system is used to prepare a film with a thickness of about 50 μm under the following conditions: Sample size: 100 mg, 250 ° C., preheating time: 2 minutes, press time: 30 seconds, A-ring spacer, and aluminum foil on both sides of the pressed film. The film was analyzed using transmission FTIR with 9 scans between 4000 and 400 cm ⁻¹ . 2736 cm ⁻¹ poly (phenylene ether) absorption is used to correct for film thickness differences between samples. Using the maximum absorption of the absorption and 2239.0Cm ^-1 between 2252.0~2224.0cm ^-1, quantified acrylonitrile. Linear regression is used to obtain a linear equation relating acrylonitrile FTIR absorption intensity to polymerized acrylonitrile residues in the composition. Poly (phenylene ether) / rubber is then formed by forming a plaque, then forming a film, measuring the acrylonitrile absorption after film thickness adjustment, and calculating the polymerized acrylonitrile residue from the acrylonitrile absorption using a calibration equation The unknown polymerized acrylonitrile residue of the modified polystyrene composition is similarly determined.

  In some embodiments, at least some of the polymerized styrene residues and at least some of the polymerized acrylonitrile residues are a group consisting of homopolystyrene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, and combinations thereof. And an acrylonitrile copolymer selected from: In some embodiments, substantially all of the polymerized acrylonitrile residues are homopolystyrene and an acrylonitrile copolymer selected from the group consisting of styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, and combinations thereof; Provided in the form of a spent recycling material. Such used recycled general purpose polystyrene (PCR GPPS) material is commercially available, for example, from Evergreen as GP-RN. Another used recycled general purpose polystyrene is obtained from the recycled refrigerator tray and is available from Hyper Cycle Systems. If homopolystyrene is provided as a used recycling material, the amount of homopolystyrene in the composition will determine the purity of the recycling material. For example, if the composition contains 60% by weight spent 90% pure recycled rubber modified polystyrene, the composition will contain 54% homopolystyrene.

  The composition does not require the compatibilized olefin-epoxy copolymer of Scobbo et al., US Pat. No. 5,264,487. As a result, the composition need not include secondary aliphatic hydroxyl groups formed upon reaction of the epoxy groups of the Scobbo compatibilized copolymer. Specifically, in some embodiments, the concentration of secondary aliphatic hydroxyl groups in the composition is 120 ppm by mass or less, specifically 100 ppm by mass or less. In some embodiments, the composition does not include secondary aliphatic hydroxyl groups. The amount of secondary aliphatic hydroxyl group residue can be determined by carbon nuclear magnetic resonance spectroscopy.

下記の構造を有するブタジエン１，４−付加の残基と、

を含むものと理解されるであろう。一部の実施形態では、重合ブタジエン残基の質量％は０．６質量％以下であり、具体的には０．５質量％以下であり、より具体的には０．３質量％以下であり、さらにより具体的には０．１質量％以下である。一部の実施形態では、該組成物は重合ブタジエン残基を含まない。重合ブタジエン残基の量は、炭素核磁気共鳴分光法によって決定できる。 In some embodiments, the composition comprises 0.7% by weight or less of polymerized butadiene residues, based on its total weight. “Polymerized butadiene residue” includes a butadiene 1,2-addition residue having the following structure:

Butadiene 1,4-addition residue having the structure:

Will be understood to include. In some embodiments, the weight percent of polymerized butadiene residues is 0.6 weight percent or less, specifically 0.5 weight percent or less, and more specifically 0.3 weight percent or less. Even more specifically, it is 0.1% by mass or less. In some embodiments, the composition does not include polymerized butadiene residues. The amount of polymerized butadiene residue can be determined by carbon nuclear magnetic resonance spectroscopy.

  In some embodiments, the composition further comprises 0.5 to 18% by weight polymerized butadiene residues, based on the total weight. Within this range, the amount of polymerized butadiene residue can be 1-14% by weight, specifically 2-9% by weight, and more specifically 3-6% by weight. The polymerized butadiene residue can be provided in various forms including rubber-modified polystyrene, block copolymers of styrene and butadiene, and combinations thereof.

重合１−ブテン残基は、ポリ（１−ブテン）、ポリ（エチレン−ｃｏ−１−ブテン）、ポリスチレン−ポリ（エチレン−ｃｏ−１−ブテン）ジブロックコポリマー（ＳＥＢ）、ポリスチレン−ポリ（エチレン−ｃｏ−１−ブテン）−ポリスチレントリブロックコポリマー（ＳＥＢＳ）およびこれらの混合物を含むポリマーの形態で組成物に供給できる。一部の実施形態では、重合１−ブテン残基は、ポリスチレン−ポリ（エチレン−ｃｏ−１−ブテン）−ポリスチレントリブロックコポリマー（ＳＥＢＳ）の形態で組成物に供給される。重合１−ブテン残基を含むポリマーの量は、組成物の合計質量に対して、１〜２０質量％であり得、具体的には２〜１５質量％であり得、より具体的には３〜１０質量％であり得、さらにより具体的には４〜８質量％であり得る。 In some embodiments, the composition further comprises 0.1 to 5 wt% polymerized 1-butene residues, based on its total weight. Within this range, the amount of polymerized 1-butene residue can be 0.2-4% by weight, specifically 0.5-3% by weight, more specifically 0.4- It may be 2% by weight. As used herein, “polymerized 1-butene residue” refers to a residue having the following structure.

Polymerized 1-butene residues include poly (1-butene), poly (ethylene-co-1-butene), polystyrene-poly (ethylene-co-1-butene) diblock copolymer (SEB), polystyrene-poly (ethylene -Co-1-butene) -polystyrene triblock copolymer (SEBS) and mixtures thereof can be supplied to the composition in the form of a polymer. In some embodiments, polymerized 1-butene residues are provided to the composition in the form of polystyrene-poly (ethylene-co-1-butene) -polystyrene triblock copolymer (SEBS). Polymerization 1—The amount of polymer containing a butene residue can be 1-20% by weight, specifically 2-15% by weight, more specifically 3%, relative to the total weight of the composition. May be -10% by weight, and more specifically 4-8% by weight.

  In some embodiments, the composition further comprises a flame retardant. A flame retardant is a compound or mixture of compounds that improves the flame retardancy of a thermoplastic composition. Suitable flame retardants include organophosphates, metal dialkyl phosphinates, nitrogen-containing flame retardants, metal hydroxides and mixtures thereof.

  In some embodiments, the flame retardant comprises an organophosphate ester. Typical organophosphate flame retardants include phosphate esters containing phenyl groups, substituted phenyl groups, or combinations thereof, and resorcinol series such as resorcinol bis (diphenyl phosphate) and bisphenol A bis (diphenyl), for example. And bisphenol-based bis-aryl phosphate esters such as phosphate). In some embodiments, the organophosphate is a tris (alkylphenyl) phosphate (eg, CAS Registry Number 89492-23-9 or 78-33-1), resorcinol bis (diphenyl phosphate). (CAS registration number 57583-54-7), bis-phenol A bis (diphenyl phosphate) (CAS registration number 181028-79-5), triphenyl phosphate (CAS registration number 115-86-6) , Tris (isopropylphenyl) phosphate (e.g. CAS Registry Number 68937-41-7) and mixtures thereof.

式中、Ｒはそれぞれ独立に、Ｃ_１−Ｃ_１２アルキレン基であり；Ｒ^５およびＲ^６はそれぞれ独立に、Ｃ_１−Ｃ_５アルキル基であり；Ｒ^１、Ｒ^２およびＲ^４は独立に、Ｃ_１−Ｃ_１２ヒドロカルビル基であり；Ｒ^３はそれぞれ独立に、Ｃ_１−Ｃ_１２ヒドロカルビル基であり；ｎは１〜２５であり；ｓ１とｓ２はそれぞれ独立に、０、１または２の整数である。一部の実施形態では、ＯＲ^１、ＯＲ^２、ＯＲ^３およびＯＲ^４は独立に、フェノール、モノアルキルフェノール、ジアルキルフェノールまたはトリアルキルフェノールから誘導される。 In some embodiments, the organophosphate comprises a bis-aryl phosphate having the structure:

In which each R is independently a C ₁ -C ₁₂ alkylene group; R ⁵ and R ⁶ are each independently a C ₁ -C ₅ alkyl group; R ¹ , R ² and R ⁴ are independently , be a _C 1 _{-C 12} hydrocarbyl group; ^{R 3} are each _{independently} a C 1 _{-C 12} hydrocarbyl group; n is 1 to 25; s1 and s2 are each independently 0, 1 or 2 It is an integer. In some embodiments, OR ¹ , OR ² , OR ³ and OR ⁴ are independently derived from phenol, monoalkylphenol, dialkylphenol or trialkylphenol.

  The bis-aryl phosphate can be derived from bisphenol. Typical bisphenols include 2,2-bis (4-hydroxyphenyl) propane (so-called bisphenol A), 2,2-bis (4-hydroxy-3-methylphenyl) propane, and bis (4-hydroxyphenyl) methane. Bis (4-hydroxy-3,5-dimethylphenyl) methane and 1,1-bis (4-hydroxyphenyl) ethane. In some embodiments, the bisphenol comprises bisphenol A.

式中、Ｒ^ａおよびＲ^ｂはそれぞれ独立にＣ_１−Ｃ_６アルキルであり；Ｍは、カルシウム、マグネシウム、アルミニウムまたは亜鉛であり；ｄは２または３である。Ｒ^ａおよびＲ^ｂの例としては、メチル、エチル、ｎ−プロピル、イソプロピル、ｎ−ブチル、ｔｅｒｔ−ブチル、ｎ−ペンチルおよびフェニルが挙げられる。一部の実施形態では、Ｒ^ａとＲ^ｂはエチルであり、Ｍはアルミニウムであり、ｄは３（すなわち、該金属ジアルキルホスフィネートはアルミニウムトリス（ジエチルホスフィネート）である。 In some embodiments, the flame retardant comprises a metal dialkyl phosphinate. As used herein, “metal dialkyl phosphinate” refers to a salt comprising at least one metal cation and at least one dialkyl phosphinate anion. In some embodiments, the metal dialkyl phosphinate has the structure:

Wherein R ^a and R ^b are each independently C ₁ -C ₆ alkyl; M is calcium, magnesium, aluminum, or zinc; d is 2 or 3. Examples of R ^a and R ^b include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl and phenyl. In some embodiments, R ^a and R ^b are ethyl, M is aluminum, and d is 3 (ie, the metal dialkyl phosphinate is aluminum tris (diethyl phosphinate).

  In some embodiments, the metal dialkyl phosphinate is particulate. The median particle size (D50) of the metal dialkyl phosphinate particles can be 40 μm or less, more specifically D50 can be 30 μm or less, and even more specifically, D50 can be 25 μm or less. A masterbatch can be formed by combining the metal dialkyl phosphinate with a polymer such as poly (phenylene ether), homopolystyrene, or a combination thereof. The concentration of metal dialkyl phosphinate in the metal dialkyl phosphinate masterbatch is generally higher than that in the thermoplastic composition. Adoption of a masterbatch that adds the metal dialkyl phosphinate to other components in the composition facilitates the addition and improves the dispersion of the metal dialkyl phosphinate.

式中、ｇは１〜約１０，０００であり、ｆ対ｇの比率は０．５：１〜１．７：１であり、具体的には０．７：１〜１．３：１であり、より具体的には０．９：１〜１．１：１である。この式が、１個または複数個のプロトンがホスフェート基（類）からメラミン基（類）に移動した種を含むことは理解されるであろう。ｇが１の場合、該窒素含有難燃剤はリン酸メラミン（ＣＡＳ登録番号第２０２０８−９５−１号）である。ｇが２の場合、該窒素含有難燃剤はピロリン酸メラミン（ＣＡＳ登録番号第１５５４１−６０−３号）である。ｇが平均で３以上の場合、該窒素含有難燃剤はポリリン酸メラミン（ＣＡＳ登録番号第５６３８６−６４−２号）である。一部の実施形態では、該窒素含有難燃剤は、ピロリン酸メラミン、ポリリン酸メラミンあるいはこれらの混合物である。該窒素含有難燃剤がポリリン酸メラミンである一部の実施形態では、ｇの平均値は２超〜１０，０００であり、具体的には５〜１，０００であり、より具体的には１０〜５００である。リン酸メラミン、ピロリン酸メラミンおよびポリリン酸メラミンの調製方法は当分野で既知であり、また、それらはすべて市販されている。例えば、ポリリン酸メラミンを、例えば、Ｋａｓｏｗｓｋｉらの米国特許第６，０２５，４１９号に記載されるように、ポリリン酸とメラミンとの反応によって、あるいは、Ｊａｃｏｂｓｏｎらの米国特許第５，９９８，５０３号に記載されるように、窒素雰囲気下、２９０℃で、ピロリン酸メラミンを恒量に達するまで加熱することによって調製できる。一部の実施形態では、該窒素含有難燃剤はメラミンシアヌレートを含む。 In some embodiments, the flame retardant comprises a nitrogen-containing flame retardant comprising a nitrogen-containing heterocyclic base and phosphoric acid, pyrophosphoric acid or polyphosphoric acid. In some embodiments, the nitrogen-containing flame retardant has the structure:

Where g is 1 to about 10,000 and the ratio of f to g is 0.5: 1 to 1.7: 1, specifically 0.7: 1 to 1.3: 1. Yes, more specifically 0.9: 1 to 1.1: 1. It will be understood that this formula includes species in which one or more protons have been transferred from a phosphate group (s) to a melamine group (s). When g is 1, the nitrogen-containing flame retardant is melamine phosphate (CAS registration number 20208-95-1). When g is 2, the nitrogen-containing flame retardant is melamine pyrophosphate (CAS registration number 15541-60-3). When g is 3 or more on average, the nitrogen-containing flame retardant is melamine polyphosphate (CAS registration number 56386-64-2). In some embodiments, the nitrogen-containing flame retardant is melamine pyrophosphate, melamine polyphosphate, or a mixture thereof. In some embodiments where the nitrogen-containing flame retardant is melamine polyphosphate, the average value of g is greater than 2 to 10,000, specifically 5 to 1,000, more specifically 10 ~ 500. Methods for preparing melamine phosphate, melamine pyrophosphate and melamine polyphosphate are known in the art and are all commercially available. For example, melamine polyphosphate may be prepared by reaction of polyphosphate with melamine, as described, for example, in Kasowski et al., US Pat. No. 6,025,419, or by Jacobson et al., US Pat. No. 5,998,503. Can be prepared by heating melamine pyrophosphate to a constant weight at 290 ° C. under a nitrogen atmosphere. In some embodiments, the nitrogen-containing flame retardant comprises melamine cyanurate.

  The nitrogen-containing flame retardant may be low volatile. For example, in some embodiments, the nitrogen-containing flame retardant is added at a rate of temperature increase of 20 ° C./min from 25 ° C. to 280 ° C., specifically from 25 ° C. to 300 ° C., more specifically from 25 ° C. to 320 ° C. The mass loss of the flame retardant by thermal mass spectrometry when heated to 0 ° C. is less than 1%.

  In some embodiments, the flame retardant comprises a metal hydroxide. Suitable metal hydroxides include all those that can impart flame retardancy, and combinations thereof. Typical metal hydroxides include magnesium hydroxide (eg CAS Registry Number 1309-42-8), aluminum hydroxide (eg CAS Registry Number 21645-51-2), cobalt hydroxide (eg CAS Registration number 21041-93-0) and combinations of these. In some embodiments, the metal hydroxide comprises magnesium hydroxide. In some embodiments, the metal hydroxide has an average particle size of 10 μm or less and / or its purity is 90% by mass or more. In some embodiments, the metal hydroxide may be substantially free of moisture, as evidenced, for example, by a mass loss upon drying at 120 ° C. × 1 hour of less than 1% by weight. desirable. In some embodiments, the metal hydroxide can be coated with, for example, stearic acid or other fatty acids.

  When the flame retardant is present in the composition, the amount thereof is 2 to 25% by mass relative to the total mass of the composition. Within this range, the amount of flame retardant can be 5-22% by weight, specifically 10-20% by weight.

  The composition may optionally exclude polymers not described herein as being necessary or optional. For example, in some embodiments, the composition comprises 1% by weight or less polyamide. The amount of polyamide may be 0.5% by weight or less, specifically 0.1% by weight or less. In some embodiments, the composition does not include a polyamide. In some embodiments, the composition comprises 1% by weight or less polyolefin. The amount of polyolefin can be 0.5% by weight or less, specifically 0.1% by weight or less. In some embodiments, the composition does not include a polyolefin.

  In a very specific embodiment, the composition is a poly (2,2) having an intrinsic viscosity of 0.35 to 0.6 dL / g measured in chloroform at 25 ° C., relative to its total weight, unless otherwise specified. 6-dimethyl-1,4-phenylene ether), 60 to 80% by mass, 5 to 15% by mass of polymerized styrene residue, 0.4 to 2% by mass of polymerized 1-butene residue, and organic phosphoric acid A flame retardant containing an ester is contained in an amount of 10 to 20% by mass and a polymerized acrylonitrile residue is contained in an amount of 0.2 to 1.2% by mass. In some embodiments, the composition comprises 0.7% by weight or less of polymerized polybutadiene residues.

  The present invention extends to methods for preparing the composition. Accordingly, unless otherwise specified, one embodiment provides poly (phenylene ether) greater than 40 to 94.8% by weight, homopolystyrene 5 to 59.8% by weight, and polymerized acrylonitrile, unless otherwise specified. Acrylonitrile homopolymer and / or copolymer in an amount sufficient to supply 0.2 to less than 1.5% by weight of residues, with a concentration of secondary aliphatic hydroxyl groups of 120% by weight. It is a formation method of a composition provided with the step of forming a composition below ppm. Within the range of greater than 40% to 94.8% by weight, the amount of poly (phenylene ether) can be greater than 41%, greater than 43%, greater than 45%, or 50%. It can also be up to 90%, up to 80%, up to 70%, up to 65%, or up to 60%. Within the range of 5-59.8% by weight, the amount of homopolystyrene can be 10-50% by weight, specifically 15-40% by weight, more specifically 15-30% by weight. It can be. Within the range of less than 0.2-1.5% by weight, the amount of polymerized acrylonitrile residue may be 0.4-1.4% by weight, specifically 0.6-1.3% by weight. It may be, more specifically 0.6 to 1.2% by weight, and even more specifically 0.6 to 1% by weight. Within the range of 120 mass ppm or less, the concentration of secondary aliphatic hydroxyl groups can be 100 mass ppm or less, or can be 50 mass ppm or less. In some embodiments, the composition comprises 0.7% by weight or less of polymerized polybutadiene residues. Within the upper limit of 0.7% by weight or less, the amount of polymerized butadiene can be 0.6% by weight or less, 0.5% by weight or less, 0.3% by weight or less, or 0 1% or less; alternatively, the composition may be substantially free of polymerized butadiene residues. In some embodiments, at least some of the polymerized acrylonitrile residues comprise homopolystyrene and an acrylonitrile copolymer selected from the group consisting of styrene-acrylonitrile copolymers, acrylonitrile-butadiene-styrene copolymers, and combinations thereof. It is provided in the form of used recycling material. In some embodiments, substantially all of the polymerized acrylonitrile residues are homopolystyrene and an acrylonitrile copolymer selected from the group consisting of styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, and combinations thereof; Provided in the form of a spent recycling material. All of the compositional variations described above in the context of the composition apply equally to the method of forming the composition.

  The invention further extends to compositions prepared or obtained by the method.

  The composition is useful for forming articles, particularly injection molded articles. Specific articles include, for example, relay boxes, electrical sockets, electrical connectors, television deflection yokes, television backs, television bezels, lighting fixtures, residential and commercial electrical wiring appliances, electrical meters and charging enclosures. In some embodiments, the injection molding conditions are barrel temperature: 250-350 ° C., specifically 270-310 ° C., mold temperature: 50-100 ° C., specifically 55-90 ° C. Illustrative injection conditions will be described in the examples below.

  The present invention includes at least the following embodiments.

  Embodiment 1: Unless otherwise specified, with respect to the total weight of the composition, the poly (phenylene ether) is more than 40 to 94.8% by weight, the polymerized styrene residue is 5 to 59.8% by weight, A composition containing 0.2 to less than 1.5% by mass of a group, wherein the concentration of secondary aliphatic hydroxyl groups is 120 ppm by mass or less.

  Embodiment 2: At least part of the polymerized styrene residue and at least part of the polymerized acrylonitrile residue are selected from the group consisting of homopolystyrene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, and combinations thereof. The composition of embodiment 1, provided in the form of a spent recycling material comprising a selected acrylonitrile copolymer.

  Embodiment 3: Substantially all of the polymerized acrylonitrile residues comprise homopolystyrene and an acrylonitrile copolymer selected from the group consisting of styrene-acrylonitrile copolymers, acrylonitrile-butadiene-styrene copolymers, and combinations thereof. The composition according to embodiment 1, provided in the form of a used recycling material.

  Embodiment 4: The composition according to embodiment 3, wherein the homopolystyrene comprises atactic homopolystyrene.

  Embodiment 5: The composition according to any one of Embodiments 1 to 4, wherein the poly (phenylene ether) comprises unused poly (phenylene ether).

  Embodiment 6: The composition according to any one of Embodiments 1 to 5, comprising 0.7% by mass or less of a polymerized butadiene residue.

  Embodiment 7: The composition according to any one of Embodiments 1 to 5, further comprising 0.5 to 18% by weight of a polymerized butadiene residue.

  Embodiment 8: The composition according to any of Embodiments 1 to 7, further comprising 0.1 to 5% by weight of polymerized 1-butene residue.

  Embodiment 9: The composition according to any one of Embodiments 1 to 8, further comprising 2 to 25% by weight of a flame retardant.

  Embodiment 10: The composition according to embodiment 9, wherein the flame retardant comprises an organophosphate.

  Embodiment 11: The composition according to any one of Embodiments 1 to 10, comprising 1% by weight or less of polyamide.

  Embodiment 12 The composition according to any of Embodiments 1 to 11, comprising no more than 1% by weight of polyolefin.

  Embodiment 13: Poly (phenylene ether) comprising poly (2,6-dimethyl-1,4-phenylene ether) having an intrinsic viscosity of 0.35-0.6 dL / g measured in chloroform at 25 ° C. 80% by mass, 5-15% by mass of the polymerized styrene residue, 0.4-2% by mass of polymerized 1-butene residue, 10-20% by mass of a flame retardant containing an organic phosphate, 2. The composition according to claim 1, comprising 0.2 to 1.2% by mass of the polymerized acrylonitrile residue, and a concentration of secondary aliphatic hydroxyl groups of 120 ppm by mass or less.

  Embodiment 13a: Poly (2,6-dimethyl-1,4- with an intrinsic viscosity of 0.35-0.6 dL / g measured in chloroform at 25 ° C., relative to the total mass of the composition, unless otherwise specified. 60 to 80% by mass of phenylene ether), 5 to 15% by mass of polymerized styrene residue, 0.4 to 2% by mass of polymerized 1-butene residue, and 10 to 10% of a flame retardant containing an organic phosphate ester. A composition comprising 20% by mass and 0.2 to 1.2% by mass of a polymerized acrylonitrile residue, wherein the concentration of secondary aliphatic hydroxyl groups is 120 mass ppm or less.

  Embodiment 14: An article comprising the composition according to any one of Embodiments 1 to 13.

  Embodiment 15: Unless otherwise specified, the poly (phenylene ether) is more than 40 to 94.8% by mass, the homopolystyrene is 5 to 59.8% by mass, and the polymerized acrylonitrile residue 0, based on the total mass of the composition. A mixture of a melt-mixed component containing a sufficient amount of acrylonitrile homopolymer and / or copolymer to provide less than 2 to 1.5% by weight, with a secondary aliphatic hydroxyl group concentration of 120 ppm by weight. A method for forming a composition comprising the step of forming the following composition.

  Embodiment 16: Use wherein at least a portion of the polymerized acrylonitrile residue comprises homopolystyrene and an acrylonitrile copolymer selected from the group consisting of styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer and combinations thereof Embodiment 16. The method of embodiment 15 provided in the form of a spent recycling material.

  Embodiment 17: Substantially all of the polymerized acrylonitrile residues comprise homopolystyrene and acrylonitrile copolymers selected from the group consisting of styrene-acrylonitrile copolymers, acrylonitrile-butadiene-styrene copolymers, and combinations thereof. Embodiment 16. The method of embodiment 15 provided in the form of a used recycling material.

  The invention is further illustrated by the following non-limiting examples.

(Examples 1-4, Reference Examples 5-7 , Comparative Examples 1-9)
These examples illustrate the performance results when acrylonitrile copolymer is added to a composition comprising poly (phenylene ether) and homopolystyrene. To simulate the effects of styrene-acrylonitrile copolymer impurities in recycled polystyrene, styrene-acrylonitrile copolymer is used.

Compositions were prepared using the ingredients listed in Table 1. Inventive and comparative examples are shown in Table 2. The unit of the component amount is mass%. In Table 2, the “SAN% in PS” row is calculated by 100 × (SAN mass%) / (PS mass% + SAN mass%). “SAN% in PS” is a proxy for the corresponding SAN mass% in the recycled homopolystyrene raw material. The composition was mixed by operating a Toshiba TEM50A twin screw extruder with an inner diameter of 53 mm at a screw speed of 280 rpm and a throughput of about 80 kg / h. In the extruder, 12 temperature control zones and a temperature control die were used. In Examples 1 and 2 and Comparative Examples 1 and 2, the temperature from the supply port to the die was set to 300 ° C / 300 ° C / 300 ° C / 300 ° C / 300 ° C / 300 ° C / 300 ° C / 300 ° C / 300 ° C / It was set as 300 degreeC / 300 degreeC / 300 degreeC / 320 degreeC. In Example 3 , Reference Examples 5 and 6 , and Comparative Examples 3 to 6, the temperature from the supply port to the die was 150 ° C / 270 ° C / 280 ° C / 280 ° C / 280 ° C / 280 ° C / 280 ° C / 280. ℃ / 280 ℃ / 280 ℃ / 280 ℃ / 280 ℃ / 290 ℃ In Reference Example 7 and Comparative Examples 7 to 9, the temperature from the supply port to the die was 250 ° C./270° C./280° C./280° C./280° C./280° C./280° C./280° C./280° C./280° C. / 280 ° C / 280 ° C / 300 ° C. All the components other than the flame retardant were added at the supply port, and the flame retardants resorcinol bis (diphenyl phosphate) and bisphenol A bis (diphenyl phosphate) were added at the zone 2 injection port. The extrudate was cooled in a water bath, pelletized, dried at 90 ° C. for 2 hours, and then used for forming a test article.

The test article for the physical property test was injection molded with a Toyo Plaster Ti-80G2 injection molding machine manufactured by Toyo Machine Metal Co., Ltd. Test articles for physical property tests of Examples 1 and 2 and Comparative Examples 1 and 2 were molded at a barrel temperature of 280 ° C. and a mold temperature of 60 ° C .. Examples 3 and 4, Reference Examples 5 to 7 and comparison Examples 3 to 9 were molded at a barrel temperature of 200 ° C. and a mold temperature of 50 ° C.

  The haze value was based on JIS K7136, and a HM-150 haze meter from Murakami Color Research Laboratory and a blend of polystyrene and polyacrylonitrile (without other components) were molded at a barrel temperature of 220 ° C. and a mold temperature of 50 ° C. 3 And 2 mm thick plate.

  Notched Izod impact strength values (kg-cm / cm) are in accordance with ASTM D256-10, temperature: 23 ° C., hammer energy: 2 J, cross-sectional dimensions: 3.2 × 12.7 mm, and length: 6. Measurement was performed using a test sample of 4 cm, a notch angle: 45 °, a material depth under the notch: 10.16 mm, and 5 test pieces per composition.

  Notched Izod impact strength retention (%) was determined for the corresponding sample without SAN addition. For example, the notched Izod impact strength retention of the inventive example 2 was calculated as 100 × 21.4 / 23.5 = 91% with respect to the value of the comparative example 1. Furthermore, the notched Izod impact strength retention rate of Example 3 was calculated as 100 × 17/17 = 100% with respect to the value of Comparative Example 3.

  From these results, a composition made of a combination of polystyrene and SAN and having an acceptable haze value (ie, 98% or less) can be used as long as the amount of polymerized acrylonitrile residues is 1.5% by mass or less. It can be seen that it has an attached Izod impact strength retention (ie, an impact strength retention of at least 85%).

Claims (10)

For the total mass of the composition,
More than 40 to 94.8% by mass of poly (phenylene ether) composed of poly (2,6-dimethyl-1,4-phenylene ether) ;
5 to 59.8% by mass of a polymerized styrene residue,
0.2 to less than 1.5% by mass of polymerized acrylonitrile residue ,
2 to 25% by weight of a flame retardant ,
The polymerized acrylonitrile residue is present in the form of a styrene-acrylonitrile copolymer;
A composition having a secondary aliphatic hydroxyl group concentration of 120 mass ppm or less.   At least a portion of the polymerized styrene residue and at least a portion of the polymerized acrylonitrile residue are selected from the group consisting of homopolystyrene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, and combinations thereof. The composition of claim 1 provided in the form of a spent recycling material comprising a copolymer. The polymerization of acrylonitrile residues, and homo polystyrene, styrene - providing styrene copolymers and acrylonitrile copolymers selected from the group consisting of these combinations, in the form of spent recycled materials comprising - acrylonitrile copolymers, acrylonitrile - butadiene The composition of claim 1, wherein:   The composition according to claim 3, wherein the homopolystyrene comprises atactic homopolystyrene.   The composition according to any one of claims 1 to 4, wherein the poly (phenylene ether) includes unused poly (phenylene ether). The composition according to any one of claims 1 to 5, further comprising 0.1 to 5% by mass of a polymerized 1-butene residue having the following structure .

60-80 mass% of poly (phenylene ether) containing poly (2,6-dimethyl-1,4-phenylene ether) having an intrinsic viscosity of 0.35-0.6 dL / g measured in chloroform at 25 ° C. ,
5-15% by mass of the polymerized styrene residue,
0.4 to 2% by mass of polymerized 1-butene residue having the following structure :

10-20% by mass of a flame retardant containing an organic phosphate,
0.2 to 1.2% by mass of the polymerized acrylonitrile residue,
The composition according to claim 1, wherein the concentration of the secondary aliphatic hydroxyl group is 120 ppm by mass or less.   An article comprising the composition according to any one of claims 1 to 7. More than 40 to 94.8% by mass of poly (phenylene ether) composed of poly (2,6-dimethyl-1,4-phenylene ether) and 5 to 59 of homopolystyrene with respect to the total mass of the composition. Melt mixing comprising 8% by weight, a sufficient amount of acrylonitrile homopolymer and / or copolymer to supply 0.2 to less than 1.5% by weight of polymerized acrylonitrile residues, and 2 to 25% by weight of a flame retardant Formed by mixing ingredients,
A method for forming a composition, wherein the concentration of secondary aliphatic hydroxyl groups is 120 mass ppm or less.   At least a portion of the polymerized acrylonitrile residues of a spent recycling material comprising homopolystyrene and an acrylonitrile copolymer selected from the group consisting of styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer and combinations thereof. The method of forming a composition according to claim 9, wherein the composition is provided in a form.